JPH10188953A - Non-aqueous electrolyte secondary battery - Google Patents
Non-aqueous electrolyte secondary batteryInfo
- Publication number
- JPH10188953A JPH10188953A JP8359248A JP35924896A JPH10188953A JP H10188953 A JPH10188953 A JP H10188953A JP 8359248 A JP8359248 A JP 8359248A JP 35924896 A JP35924896 A JP 35924896A JP H10188953 A JPH10188953 A JP H10188953A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- lithium
- carbonate
- secondary battery
- electrolyte secondary
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、各種電子機器の電
源として使用される充放電可能な非水電解液二次電池に
関し、特にその正極が改良された非水電解液二次電池に
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a chargeable / dischargeable nonaqueous electrolyte secondary battery used as a power source for various electronic devices, and more particularly to a nonaqueous electrolyte secondary battery having an improved positive electrode.
【０００２】[0002]
【従来の技術】近年、種々の電子機器の飛躍的進歩と共
に、長時間便利に、かつ経済的に使用できる電源として
再充電可能な二次電池の研究が進められている。代表的
な二次電池としては、鉛蓄電池、アルカリ蓄電池、リチ
ウム二次電池等が知られている。これらの二次電池の中
でも、特にリチウム二次電池は、出力が高く、エネルギ
ー密度も高い等の利点を有している。2. Description of the Related Art In recent years, along with the remarkable progress of various electronic devices, research on a rechargeable secondary battery as a power source that can be used conveniently and economically for a long time has been advanced. As typical secondary batteries, lead storage batteries, alkaline storage batteries, lithium secondary batteries, and the like are known. Among these secondary batteries, a lithium secondary battery has advantages such as high output and high energy density.
【０００３】ところで、リチウム二次電池は、リチウム
イオンと可逆的に電気化学反応する活物質を用いた正極
と、金属リチウム、あるいはリチウムを含む負極と非水
電解液とから構成されている。そして、リチウム二次電
池の放電反応は、一般に、負極においてリチウムイオン
が非水電解液中に溶出し、正極では活物質の層間等にリ
チウムイオンがインターカレーションすることによって
進行する。逆に、充電する場合には、上記の逆反応が進
行し、正極においてはリチウムイオンがデインターカレ
ーションする。従って、リチウム二次電池においては、
負極から供給されるリチウムイオンが正極活物質に出入
りする反応に基づき充放電が繰り返されることになる。A lithium secondary battery is composed of a positive electrode using an active material that reversibly electrochemically reacts with lithium ions, metallic lithium or a negative electrode containing lithium, and a non-aqueous electrolyte. In general, the discharge reaction of a lithium secondary battery proceeds when lithium ions are eluted into a non-aqueous electrolyte at a negative electrode and lithium ions intercalate between layers of an active material at a positive electrode. Conversely, when charging, the reverse reaction proceeds, and lithium ions are deintercalated at the positive electrode. Therefore, in a lithium secondary battery,
Charging and discharging are repeated based on a reaction in which lithium ions supplied from the negative electrode enter and exit the positive electrode active material.
【０００４】一般に、リチウム二次電池の負極活物質と
しては、金属リチウム、リチウム合金（例えば、Ｌｉ−
Ａｌ合金）、リチウムをドープした導電性高分子（例え
ば、ポリアセチレンやポリピロール等）、リチウムイオ
ンを結晶中に取り込んだ層間化合物等が用いられてい
る。一方、正極活物質には、金属酸化物、金属硫化物、
あるいはポリマー等が用いられ、例えば、ＴｉＳ2、Ｍ
ｏＳ2、ＮｂＳｅ2、Ｖ2Ｏ5等が知られているが、近年で
は、高い放電電位と高いエネルギー密度とを有する正極
活物質として、ＬｉxＣｏyＯ2（ここで、ｘの値は充放
電によって変化するが、通常、合成時にはｘ及びｙはそ
れぞれ約１である。）を用いた非水電解液二次電池が実
用化されている。In general, as a negative electrode active material of a lithium secondary battery, lithium metal, a lithium alloy (for example, Li-
For example, a conductive polymer doped with lithium (for example, polyacetylene or polypyrrole), an interlayer compound in which lithium ions are incorporated in a crystal, or the like is used. On the other hand, positive electrode active materials include metal oxides, metal sulfides,
Alternatively, a polymer or the like is used, for example, TiS 2 , M
Although oS 2 , NbSe 2 , V 2 O 5 and the like are known, in recent years, as a positive electrode active material having a high discharge potential and a high energy density, Li x Co y O 2 (where x has a value of x A non-aqueous electrolyte secondary battery using a non-aqueous electrolyte secondary battery, which varies depending on charging and discharging, but generally each of x and y is about 1 at the time of synthesis, has been put to practical use.
【０００５】しかしながら、この複合酸化物の原材料で
あるコバルトは、資源的に希少であり、また商業的に利
用可能な鉱床が数少ない国に偏在しているため高価で価
格変動が大きく、かつ将来的には供給不安の伴うもので
ある。このため、リチウム二次電池の広範囲な普及を計
る上で、コバルトより安価で資源的にも豊富な原材料か
ら構成され、且つリチウムコバルト複合酸化物に比べ性
能的にも見劣りしない正極活物質として、ＬｉＮｉＯ2
あるいはＬｉＭｎ2Ｏ4の使用が検討されている。特に、
マンガンは、コバルトのみならずニッケルに比べても安
価であり、資源的にも豊富である。また、マンガン乾電
池、アルカリマンガン乾電池、リチウム１次電池の材料
として、二酸化マンガンは大量に流通しており、材料供
給の面からも不安の少ない材料である。このため、マン
ガンを原料とする非水電解液二次電池の正極活物質とし
てのリチウムマンガン複合酸化物の研究が近年盛んに行
われている。中でも、スピネル型構造のリチウムマンガ
ン複合酸化物は、電気化学的に酸化されるとリチウムに
対し３Ｖ以上の電位を示し、１４８ｍＡｈ／ｇの理論充
放電容量を持つ材料であることが報告されている。[0005] However, cobalt, which is a raw material of this composite oxide, is scarce in resources and is expensive, has large price fluctuations due to the uneven distribution of commercially available ore deposits in a few countries. Is accompanied by supply anxiety. For this reason, in order to promote the widespread use of lithium secondary batteries, as a positive electrode active material composed of raw materials that are cheaper and more resource-rich than cobalt and that are not inferior in performance compared to lithium-cobalt composite oxide, LiNiO 2
Alternatively, use of LiMn 2 O 4 is being studied. Especially,
Manganese is cheaper than nickel as well as cobalt, and is rich in resources. In addition, manganese dioxide is distributed in large quantities as a material for manganese dry batteries, alkaline manganese dry batteries, and lithium primary batteries, and is a material with little concern from the viewpoint of material supply. For this reason, research on a lithium manganese composite oxide as a positive electrode active material of a non-aqueous electrolyte secondary battery using manganese as a raw material has been actively conducted in recent years. Above all, it has been reported that a lithium manganese composite oxide having a spinel structure has a potential of 3 V or more with respect to lithium when electrochemically oxidized, and is a material having a theoretical charge / discharge capacity of 148 mAh / g. .
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、マンガ
ン酸化物、あるいはリチウムマンガン複合酸化物を正極
活物質として用いたリチウムイオン非水電解液二次電池
には、充放電サイクルに伴い電池性能が劣化するという
欠点があった。特に、高温、即ち室温を超える温度環境
下で使用した場合にその劣化が著しいものとなってい
た。However, in a lithium ion nonaqueous electrolyte secondary battery using manganese oxide or lithium manganese composite oxide as a positive electrode active material, battery performance deteriorates with charge / discharge cycles. There was a disadvantage. In particular, when used in a high temperature environment, that is, a temperature environment exceeding room temperature, the deterioration has been remarkable.
【０００７】高温での電池性能の劣化の問題は、電気自
動車用あるいはロードレベリング用の大型の非水電解液
二次電池の場合には特に留意すべき問題となっている。
これは、電池が大型化すればするほど、使用時の内部発
熱が無視できなくなり、周囲の環境温度が室温付近であ
っても電池内部は比較的高温となる可能性が増大するた
めである。また、この問題は、小型携帯機器用等として
使用される比較的小型の電池であっても、真夏の自動車
の車室内等の高温環境で使用されることも考慮すれば無
視できるものではない。The problem of deterioration of battery performance at high temperatures is a problem to be especially noted in the case of a large non-aqueous electrolyte secondary battery for electric vehicles or load leveling.
This is because as the size of the battery increases, the internal heat generation during use cannot be ignored and the possibility that the inside of the battery becomes relatively high even when the ambient temperature is around room temperature increases. In addition, this problem is not negligible even if a relatively small battery used for a small portable device or the like is used in a high-temperature environment such as a cabin of a car in midsummer.
【０００８】本発明は、以上の従来の技術の課題を解決
しようとするものであり、安価で資源的に豊富な原材料
であるマンガン酸化物又はリチウムとマンガンとの複合
酸化物から形成した正極を使用する非水電解液二次電池
の、室温を超える温度条件下における電池特性（例え
ば、充放電サイクル特性）を改善することを目的とす
る。An object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a positive electrode formed from manganese oxide or a composite oxide of lithium and manganese, which is an inexpensive and resource-rich raw material. An object of the present invention is to improve battery characteristics (for example, charge / discharge cycle characteristics) of a nonaqueous electrolyte secondary battery to be used under a temperature condition exceeding room temperature.
【０００９】[0009]
【課題を解決するための手段】本発明者は、マンガン酸
化物又はリチウムマンガン複合酸化物と導電剤とバイン
ダーとからなる正極合剤（乾燥状態）に特定重量％範囲
のアルカリ金属炭酸塩を含有させることにより、上述の
目的を達成できることを見出し、本発明を完成させるに
至った。Means for Solving the Problems The present inventor has disclosed that a positive electrode mixture (dry state) comprising a manganese oxide or a lithium manganese composite oxide, a conductive agent and a binder contains a specific weight% range of an alkali metal carbonate. By doing so, the inventors have found that the above-mentioned object can be achieved, and have completed the present invention.
【００１０】即ち、本発明は、マンガン酸化物又はリチ
ウムとマンガンとの複合酸化物を含む正極合剤から形成
された正極と、リチウム金属負極又はリチウムを含む負
極と、非水電解液とからなる非水電解液二次電池におい
て、正極合剤中に乾燥重量換算でアルカリ金属炭酸塩が
０．５〜２０重量パーセント含有されていることを特徴
とする非水電解液二次電池を提供する。That is, the present invention comprises a positive electrode formed from a positive electrode mixture containing manganese oxide or a composite oxide of lithium and manganese, a lithium metal negative electrode or a negative electrode containing lithium, and a nonaqueous electrolyte. Provided is a non-aqueous electrolyte secondary battery, wherein the alkali metal carbonate is contained in the positive electrode mixture in an amount of 0.5 to 20% by weight in terms of dry weight.
【００１１】[0011]
【発明の実施の形態】以下、本発明を詳細に説明する。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
【００１２】本発明の非水電解液二次電池は、マンガン
酸化物又はリチウムマンガン複合酸化物を正極活物質と
し、それらを含む正極合剤から形成された正極と、リチ
ウム金属負極又はリチウムを含む負極と、非水電解液と
から構成されている。ここで、正極合剤中にはアルカリ
金属炭酸塩が含有されている。このように、アルカリ金
属炭酸塩を正極成分の一つとして使用することにより、
室温を超える温度条件下における電池特性（例えば、充
放電サイクル特性）を改善することができる。この理由
は必ずしも明確ではないが、非水電解液中に存在する微
量の酸性不純物あるいは充放電に伴い非水電解液中に生
ずる物質と、正極合剤中に添加したアルカリ金属炭酸塩
が選択的に反応することにより、正極活物質とそれら不
純物等との反応による正極活物質の劣化を抑制している
のではないかと考えられる。The nonaqueous electrolyte secondary battery of the present invention comprises a positive electrode formed from a positive electrode mixture containing manganese oxide or lithium manganese composite oxide as a positive electrode active material, and a lithium metal negative electrode or lithium. It is composed of a negative electrode and a non-aqueous electrolyte. Here, the positive electrode mixture contains an alkali metal carbonate. Thus, by using an alkali metal carbonate as one of the positive electrode components,
Battery characteristics (eg, charge / discharge cycle characteristics) under temperature conditions exceeding room temperature can be improved. The reason for this is not necessarily clear, but the trace amount of acidic impurities present in the non-aqueous electrolyte or the substances generated in the non-aqueous electrolyte due to charge and discharge, and the alkali metal carbonate added to the positive electrode mixture are selective. Is considered to suppress the deterioration of the positive electrode active material due to the reaction between the positive electrode active material and the impurities and the like.
【００１３】本発明において使用できる好ましいアルカ
リ金属炭酸塩としては、炭酸リチウムと炭酸ナトリウム
とを挙げることができる。これらは単独で使用してもよ
いし、混合して使用することもできる。Preferred alkali metal carbonates that can be used in the present invention include lithium carbonate and sodium carbonate. These may be used alone or as a mixture.
【００１４】乾燥状態の正極合剤中のアルカリ金属炭酸
塩の含有量は、０．５〜２０重量％、好ましくは０．５
〜１０重量％である。この範囲を下回ると十分な効果が
得られず、逆に超えると相対的に正極活物質の使用量が
減少して実用的な電池容量が得られないためである。The content of the alkali metal carbonate in the dried positive electrode mixture is 0.5 to 20% by weight, preferably 0.5 to 20% by weight.
-10% by weight. If the amount is less than the above range, a sufficient effect cannot be obtained. If the amount exceeds the range, the amount of the positive electrode active material is relatively reduced, and a practical battery capacity cannot be obtained.
【００１５】アルカリ金属炭酸塩以外の正極合剤の成分
としては、正極活物質としてマンガン酸化物又はリチウ
ムマンガン複合酸化物、導電材及びバインダーを挙げる
ことができる。As components of the positive electrode mixture other than the alkali metal carbonate, a manganese oxide or a lithium manganese composite oxide, a conductive material and a binder can be exemplified as a positive electrode active material.
【００１６】マンガン酸化物としては、二酸化マンガン
を好ましく挙げることができる。また、リチウムマンガ
ン複合酸化物としてはスピネル型結晶構造を有するもの
を好ましく挙げることができる。As the manganese oxide, manganese dioxide can be preferably mentioned. As the lithium manganese composite oxide, those having a spinel type crystal structure can be preferably mentioned.
【００１７】また、上述したように、マンガン酸化物又
はリチウムマンガン複合酸化物を正極活物質として使用
して非水電解液二次電池を構成した場合、負極活物質等
の種類や状態にもよるが、放電電圧を３Ｖ以上にするこ
とができ、高出力、高エネルギー密度の電池が得られ
る。Further, as described above, when a non-aqueous electrolyte secondary battery is constructed using manganese oxide or lithium manganese composite oxide as a positive electrode active material, it depends on the type and state of the negative electrode active material and the like. However, the discharge voltage can be set to 3 V or more, and a battery with high output and high energy density can be obtained.
【００１８】導電材としては、公知の導電材、例えばカ
ーボンブラックを使用することができる。また、バイン
ダーとしても公知のバインダー、例えばポリフッ化ビニ
リデン等を使用することができる。As the conductive material, a known conductive material, for example, carbon black can be used. As the binder, a known binder such as polyvinylidene fluoride can be used.
【００１９】本発明の非水電解液二次電池の正極は、上
述したような成分をＤＭＦなどの有機溶剤に十分に分散
させて正極合剤スラリーとし、集電体に塗布し乾燥する
ことにより作製することができる。あるいは正極合剤ス
ラリーを乾燥し粉砕して得た正極合剤粉末を集電体と共
にプレス成形することにより作製することができる。The positive electrode of the non-aqueous electrolyte secondary battery of the present invention is obtained by sufficiently dispersing the above-mentioned components in an organic solvent such as DMF to form a positive electrode mixture slurry, applying the slurry to a current collector, and drying. Can be made. Alternatively, the positive electrode mixture slurry can be produced by drying and pulverizing the positive electrode mixture slurry and press-molding the positive electrode mixture powder together with the current collector.
【００２０】本発明の非水電解液二次電池においては、
負極としては、リチウム金属、リチウムアルミニウム合
金、あるいはリチウムイオンをドープ且つ脱ドープ可能
な炭素質材料にリチウムイオンを保持させたもの等を挙
げることができる。In the non-aqueous electrolyte secondary battery of the present invention,
Examples of the negative electrode include lithium metal, a lithium aluminum alloy, and a lithium ion-doped and undoped carbonaceous material in which lithium ions are retained.
【００２１】本発明の非水電解液二次電池において使用
する非水電解液の非水溶媒としては、従来より種々の非
水電解液二次電池において使用されている非水溶媒を好
ましく使用することができる。例えば、リチウムイオン
非水電解液二次電池の場合には、高誘電率溶媒である炭
酸プロピレン、炭酸エチレン、炭酸ブチレン、γ−ブチ
ロラクトン等や、低粘度溶媒である１，２−ジメトキシ
エタン、２−メチルテトラヒドロフラン、炭酸ジメチ
ル、炭酸メチルエチル、炭酸ジエチル等を使用すること
ができる。As the non-aqueous solvent of the non-aqueous electrolyte used in the non-aqueous electrolyte secondary battery of the present invention, non-aqueous solvents conventionally used in various non-aqueous electrolyte secondary batteries are preferably used. be able to. For example, in the case of a lithium ion nonaqueous electrolyte secondary battery, propylene carbonate, ethylene carbonate, butylene carbonate, γ-butyrolactone, etc., which are high dielectric constant solvents, and 1,2-dimethoxyethane, which is a low viscosity solvent, are used. -Methyltetrahydrofuran, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate and the like can be used.
【００２２】以上のような非水溶媒に溶解させて非水電
解液を調製する際に使用する電解質としては、一般に、
伝導イオン種により異なるが、伝導イオン種がリチウム
イオンである場合にはＬｉＣｌＯ4、ＬｉＡｓＦ6、Ｌｉ
ＰＦ6、ＬｉＢＦ4、ＣＦ3ＳＯ3Ｌｉ等を好ましく使用す
ることができる。これらは単独でも２種類以上を混合し
て用いることができる。The electrolyte used when preparing the non-aqueous electrolyte by dissolving the above-mentioned non-aqueous solvent is generally
Although it depends on the conductive ion species, when the conductive ion species is lithium ion, LiClO 4 , LiAsF 6 , Li
PF 6 , LiBF 4 , CF 3 SO 3 Li and the like can be preferably used. These can be used alone or in combination of two or more.
【００２３】本発明の非水電解液二次電池のセパレー
タ、電池缶、ＰＴＣ素子等に他の構成については、従来
のリチウムイオン非水電解液二次電池などと同様とする
ことができる。Other configurations of the separator, battery can, PTC element and the like of the nonaqueous electrolyte secondary battery of the present invention can be the same as those of the conventional lithium ion nonaqueous electrolyte secondary battery.
【００２４】本発明の非水電解液二次電池は、正極合剤
にアルカリ金属炭酸塩を含有させた以外は、従来の非水
電解液二次電池を製造する場合と同様に製造することが
できる。The non-aqueous electrolyte secondary battery of the present invention can be manufactured in the same manner as the conventional non-aqueous electrolyte secondary battery, except that the positive electrode mixture contains an alkali metal carbonate. it can.
【００２５】なお、本発明の非水電解液二次電池の電池
形状については特に限定されず、必要に応じて円筒型形
状、角型形状、コイン型形状、ボタン型形状等の種々の
形状とすることができる。The shape of the non-aqueous electrolyte secondary battery of the present invention is not particularly limited, and various shapes such as a cylindrical shape, a square shape, a coin shape, and a button shape may be used as necessary. can do.
【００２６】[0026]
【実施例】以下、本発明を実施例により具体的に説明す
る。The present invention will be described below in more detail with reference to examples.
【００２７】実施例１〜４及び比較例１は、スピネル型
リチウムマンガン複合酸化物（ＬｉＭｎ2Ｏ4）を正極に
含み、アルカリ金属炭酸塩として炭酸リチウムを使用し
た場合の効果を示すための例である。また、実施例５〜
８及び比較例２は、スピネル型リチウムマンガン複合酸
化物（ＬｉＭｎ2Ｏ4）を正極に含み、アルカリ金属炭酸
塩として炭酸ナトリウムを使用した場合の効果を示すた
めの例である。Examples 1 to 4 and Comparative Example 1 are examples for showing the effect when lithium carbonate is used as the alkali metal carbonate in which the positive electrode contains spinel-type lithium manganese composite oxide (LiMn 2 O 4 ). It is. Examples 5 to
8 and Comparative Example 2 are examples for showing the effect when sodium carbonate is used as the alkali metal carbonate, in which the positive electrode contains spinel-type lithium manganese composite oxide (LiMn 2 O 4 ).
【００２８】実施例１ 市販の炭酸マンガン（ＭｎＣＯ3）粉末と炭酸リチウム
（Ｌｉ2ＣＯ3）粉末とを、メノウ乳鉢を用いて混合し
た。この際の混合比は、Ｌｉ／Ｍｎ＝１／２となるよう
にした。この混合粉末を電気炉を用いて常圧の空気中で
８００℃で加熱することでリチウムマンガン複合酸化物
を得た。この試料を粉末Ｘ線回折により解析したとこ
ろ、ＩＳＤＤカード３５−７８２に記載のＬｉＭｎ2Ｏ4
のデータに一致した。Example 1 Commercially available manganese carbonate (MnCO 3 ) powder and lithium carbonate (Li 2 CO 3 ) powder were mixed using an agate mortar. The mixing ratio at this time was set so that Li / Mn = 1/2. This mixed powder was heated at 800 ° C. in air at normal pressure using an electric furnace to obtain a lithium manganese composite oxide. When this sample was analyzed by powder X-ray diffraction, LiMn 2 O 4 described in ISDD card 35-782 was analyzed.
Data.
【００２９】得られたリチウムマンガン複合酸化物粉末
に、炭酸リチウム（Ｌｉ2ＣＯ3）粉末と、導電材として
グラファイトと、バインダーとしてポリフッ化ビニリデ
ンとを混合し、更にジメチルホルムアミドを適宣滴下し
て十分に混練した。この混練物を乾燥させ、乾燥物を粉
砕することにより正極合剤粉末を得た。このとき、乾燥
状態の正極合剤中の炭酸リチウムの含有量は０．５重量
％であった。To the obtained lithium manganese composite oxide powder, lithium carbonate (Li 2 CO 3 ) powder, graphite as a conductive material, and polyvinylidene fluoride as a binder were mixed, and dimethylformamide was added dropwise as appropriate. Kneaded well. The kneaded product was dried, and the dried product was pulverized to obtain a positive electrode mixture powder. At this time, the content of lithium carbonate in the dried positive electrode mixture was 0.5% by weight.
【００３０】得られた正極合剤粉末をアルミニウムメッ
シュと共に加圧成形した。この成形体を正極とし、リチ
ウムを負極とし、６フッ化リン酸リチウム（１モル／
ｌ）のプロピレンカーボネート溶液を電解液としてコイ
ン型電池を作製した。The obtained positive electrode mixture powder was pressed together with an aluminum mesh. The molded body is used as a positive electrode, lithium is used as a negative electrode, and lithium hexafluorophosphate (1 mol /
A coin-type battery was prepared using the propylene carbonate solution of 1) as an electrolytic solution.
【００３１】実施例２ 乾燥状態の正極合剤中の炭酸リチウムの含有量を５重量
％とする以外は、実施例１と同様にして正極合剤粉末を
調製し、更にコイン型電池を作製した。Example 2 A positive electrode mixture powder was prepared in the same manner as in Example 1 except that the content of lithium carbonate in the dried positive electrode mixture was 5% by weight, and a coin-type battery was further produced. .
【００３２】実施例３ 乾燥状態の正極合剤中の炭酸リチウムの含有量を１０重
量％とする以外は、実施例１と同様にして正極合剤粉末
を調製し、更にコイン型電池を作製した。Example 3 A positive electrode mixture powder was prepared in the same manner as in Example 1 except that the content of lithium carbonate in the dried positive electrode mixture was 10% by weight, and a coin-type battery was further produced. .
【００３３】実施例４ 乾燥状態の正極合剤中の炭酸リチウムの含有量を２０重
量％とする以外は、実施例１と同様にして正極合剤粉末
を調製し、更にコイン型電池を作製した。Example 4 A positive electrode mixture powder was prepared in the same manner as in Example 1 except that the content of lithium carbonate in the dried positive electrode mixture was 20% by weight, and a coin-type battery was further produced. .
【００３４】比較例１ 正極合剤中に炭酸リチウムを含有させない以外は、実施
例１と同様にして正極合剤粉末を調製し、更にコイン型
電池を作製した。Comparative Example 1 A positive electrode mixture powder was prepared in the same manner as in Example 1 except that lithium carbonate was not contained in the positive electrode mixture, and a coin-type battery was further produced.
【００３５】（評価）実施例１〜４及び比較例１で作製
したコイン型電池について、電池温度６０℃の加速試験
条件下で充放電サイクル試験を行った。この際、電流密
度０．２７ｍＡ／ｃｍ2で４．２Ｖまで充電した後、引
き続き満充電まで４．２Ｖ定電圧充電を行った（定電流
定電圧放電）。次に放電電圧が３．７Ｖになるまで放電
を行った。この充放電サイクル試験において、サイクル
毎の容量保持率（初回サイクルの放電容量に対する各サ
イクル時の放電容量の比率）を求め、その結果を図１に
示した。(Evaluation) A charge / discharge cycle test was performed on the coin batteries manufactured in Examples 1 to 4 and Comparative Example 1 under the conditions of an acceleration test at a battery temperature of 60 ° C. At this time, after the battery was charged to 4.2 V at a current density of 0.27 mA / cm 2 , the battery was continuously charged at a constant voltage of 4.2 V until the battery was fully charged (constant current constant voltage discharge). Next, discharge was performed until the discharge voltage reached 3.7V. In this charge / discharge cycle test, the capacity retention rate for each cycle (the ratio of the discharge capacity in each cycle to the discharge capacity in the first cycle) was determined, and the results are shown in FIG.
【００３６】図１から、実施例１〜４で作製した非水電
解液二次電池は、比較例１で作製した電池に比べて、充
放電サイクルに伴う放電容量の劣化が抑制されていたこ
とがわかる。From FIG. 1, it can be seen that the non-aqueous electrolyte secondary batteries prepared in Examples 1 to 4 were more resistant to the deterioration of the discharge capacity due to the charge / discharge cycle than the battery prepared in Comparative Example 1. I understand.
【００３７】また、図１における実施例３と実施例４と
の結果から、炭酸リチウムを、正極合剤（乾燥状態）の
２０重量パーセントを超える量で含有させても大きな添
加効果が見込めないことが予測できる。しかも、炭酸リ
チウムの含有量を増加させると正極活物質の含有量が相
対的に減少して電池容量が低下する。従って、炭酸リチ
ウムの配合量を、正極合剤（乾燥状態）の２０重量パー
セント以下とすることが好ましいことがわかる。Further, from the results of Example 3 and Example 4 in FIG. 1, a large addition effect cannot be expected even if lithium carbonate is contained in an amount exceeding 20% by weight of the positive electrode mixture (dry state). Can be predicted. In addition, when the content of lithium carbonate is increased, the content of the positive electrode active material is relatively reduced, and the battery capacity is reduced. Therefore, it is understood that the amount of lithium carbonate is preferably set to 20% by weight or less of the positive electrode mixture (dry state).
【００３８】一方、実施例１と比較例１との結果から、
炭酸リチウムを正極合剤（乾燥状態）の０．５重量パー
セント以上いれないと、十分な添加効果が得られないこ
とがわかる。On the other hand, from the results of Example 1 and Comparative Example 1,
It can be seen that a sufficient addition effect cannot be obtained unless lithium carbonate is added in an amount of 0.5% by weight or more of the positive electrode mixture (dry state).
【００３９】以上のことから、正極合剤（乾燥状態）中
の炭酸リチウムの含有量を０．５〜２０重量％とするこ
とが合理的であることがわかる。From the above, it can be seen that it is reasonable to set the content of lithium carbonate in the positive electrode mixture (dry state) to 0.5 to 20% by weight.
【００４０】実施例５〜８及び比較例２ 炭酸リチウムに代えて炭酸ナトリウムを使用する以外
は、実施例１〜４及び比較例１を繰り返して正極合剤を
調製し、コイン型の非水電解液二次電池を作製した。得
られたコイン型非水二次電池について、実施例１と同様
に充放電サイクル試験を行い、その結果を図２に示し
た。Examples 5 to 8 and Comparative Example 2 A positive electrode mixture was prepared by repeating Examples 1 to 4 and Comparative Example 1 except that sodium carbonate was used instead of lithium carbonate. A liquid secondary battery was manufactured. The obtained coin-type nonaqueous secondary battery was subjected to a charge / discharge cycle test in the same manner as in Example 1, and the results are shown in FIG.
【００４１】図２から、実施例５〜８で作製した非水電
解液二次電池は、比較例２で作製した電池に比べて、充
放電サイクルに伴う放電容量の劣化が抑制されていたこ
とがわかる。FIG. 2 shows that the non-aqueous electrolyte secondary batteries produced in Examples 5 to 8 were more resistant to the deterioration of the discharge capacity due to the charge / discharge cycle than the batteries produced in Comparative Example 2. I understand.
【００４２】また、図２における実施例７と実施例８と
の結果から、炭酸ナトリウムを、正極合剤（乾燥状態）
の２０重量パーセントを超える量で含有させても大きな
添加効果が見込めないことが予測できる。しかも、炭酸
ナトリウムの含有量を増加させると正極活物質の含有量
が相対的に減少して電池容量が低下する。従って、炭酸
リチウムの配合量を、正極合剤（乾燥状態）の２０重量
パーセント以下とすることが好ましいことがわかる。From the results of Example 7 and Example 8 in FIG. 2, sodium carbonate was added to the positive electrode mixture (dry state).
It can be expected that a large addition effect cannot be expected even if it is contained in an amount exceeding 20% by weight. In addition, when the content of sodium carbonate is increased, the content of the positive electrode active material is relatively reduced, and the battery capacity is reduced. Therefore, it is understood that the amount of lithium carbonate is preferably set to 20% by weight or less of the positive electrode mixture (dry state).
【００４３】一方、実施例５と比較例２との結果から、
炭酸ナトリウムを正極合剤（乾燥状態）の０．５重量パ
ーセント以上いれないと、十分な添加効果が得られない
ことがわかる。On the other hand, from the results of Example 5 and Comparative Example 2,
It can be seen that a sufficient effect cannot be obtained unless sodium carbonate is added in an amount of 0.5% by weight or more of the positive electrode mixture (dry state).
【００４４】以上のことから、正極合剤（乾燥状態）中
の炭酸ナトリウムの含有量を０．５〜２０重量％とする
ことが合理的であることがわかる。From the above, it can be seen that it is reasonable to set the content of sodium carbonate in the positive electrode mixture (dry state) to 0.5 to 20% by weight.
【００４５】[0045]
【発明の効果】本発明によれば、安価で資源的に豊富な
原材料でであるマンガン酸化物又はリチウムとマンガン
との複合酸化物から形成した正極を使用する非水電解液
二次電池の、室温を超える温度条件下における電池特性
（例えば、充放電サイクル特性）を改善することができ
る。According to the present invention, there is provided a non-aqueous electrolyte secondary battery using a positive electrode formed from manganese oxide or a composite oxide of lithium and manganese, which is an inexpensive and resource-rich raw material. Battery characteristics (eg, charge / discharge cycle characteristics) under temperature conditions exceeding room temperature can be improved.
【図１】実施例１〜４及び比較例１で作製したコイン型
非水電解液二次電池の充放電サイクル時のサイクル数と
放電容量維持率との関係図である。FIG. 1 is a graph showing the relationship between the number of charge / discharge cycles and the discharge capacity retention ratio of the coin-type nonaqueous electrolyte secondary batteries produced in Examples 1 to 4 and Comparative Example 1.
【図２】実施例５〜８及び比較例２で作製したコイン型
非水電解液二次電池の充放電サイクル時のサイクル数と
放電容量維持率との関係図である。FIG. 2 is a graph showing the relationship between the number of charge / discharge cycles and the discharge capacity retention ratio of the coin-type nonaqueous electrolyte secondary batteries produced in Examples 5 to 8 and Comparative Example 2.
Claims (4)
合酸化物を含む正極合剤から形成された正極と、リチウ
ム金属負極又はリチウムを含む負極と、非水電解液とか
らなる非水電解液二次電池において、乾燥状態の正極合
剤中にアルカリ金属炭酸塩が０．５〜２０重量パーセン
ト含有されていることを特徴とする非水電解液二次電
池。1. A nonaqueous electrolyte secondary battery comprising a positive electrode formed from a positive electrode mixture containing manganese oxide or lithium manganese composite oxide, a lithium metal negative electrode or a negative electrode containing lithium, and a nonaqueous electrolyte. 3. The non-aqueous electrolyte secondary battery according to claim 1, wherein the positive electrode mixture in a dry state contains 0.5 to 20% by weight of an alkali metal carbonate.
炭酸ナトリウムである請求項１記載の非水電解液二次電
池。2. The non-aqueous electrolyte secondary battery according to claim 1, wherein the alkali metal carbonate is lithium carbonate or sodium carbonate.
型結晶構造を有する請求項１又は２記載の非水電解液二
次電池。3. The non-aqueous electrolyte secondary battery according to claim 1, wherein the lithium-manganese composite oxide has a spinel-type crystal structure.
のいずれかに記載の非水電解液二次電池。4. The discharge voltage according to claim 1, wherein the discharge voltage is 3 V or more.
The non-aqueous electrolyte secondary battery according to any one of the above.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35924896A JP3562187B2 (en) | 1996-12-27 | 1996-12-27 | Non-aqueous electrolyte secondary battery |
| US08/996,320 US6022641A (en) | 1996-12-27 | 1997-12-22 | Non-aqueous electrolyte secondary cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35924896A JP3562187B2 (en) | 1996-12-27 | 1996-12-27 | Non-aqueous electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10188953A true JPH10188953A (en) | 1998-07-21 |
| JP3562187B2 JP3562187B2 (en) | 2004-09-08 |
Family
ID=18463526
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35924896A Expired - Fee Related JP3562187B2 (en) | 1996-12-27 | 1996-12-27 | Non-aqueous electrolyte secondary battery |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US6022641A (en) |
| JP (1) | JP3562187B2 (en) |
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| JP2002117843A (en) * | 2000-10-05 | 2002-04-19 | Sony Corp | Nonaqueous electrolyte secondary battery |
| JP2008181830A (en) * | 2007-01-26 | 2008-08-07 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery |
| JP2011159576A (en) * | 2010-02-03 | 2011-08-18 | Hitachi Maxell Energy Ltd | Lithium ion secondary battery |
| KR20130121132A (en) * | 2010-11-25 | 2013-11-05 | 바스프 에스이 | Process for preparing precursors for transition metal mixed oxides |
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| TW434923B (en) * | 1998-02-20 | 2001-05-16 | Hitachi Ltd | Lithium secondary battery and liquid electrolyte for the battery |
| US6291537B1 (en) * | 2000-03-28 | 2001-09-18 | The United States Of America As Represented By The Secretary Of The Air Force | Encapsulation of oxidants for pitch stabilization |
| JP4106644B2 (en) * | 2000-04-04 | 2008-06-25 | ソニー株式会社 | Battery and manufacturing method thereof |
| US7799751B2 (en) * | 2000-12-14 | 2010-09-21 | The Clorox Company | Cleaning composition |
| US20030100465A1 (en) * | 2000-12-14 | 2003-05-29 | The Clorox Company, A Delaware Corporation | Cleaning composition |
| US20020183233A1 (en) * | 2000-12-14 | 2002-12-05 | The Clorox Company, Delaware Corporation | Bactericidal cleaning wipe |
| US6558844B2 (en) | 2001-01-31 | 2003-05-06 | Wilmont F. Howard, Jr. | Stabilized spinel battery cathode material and methods |
| US7078129B2 (en) * | 2002-01-11 | 2006-07-18 | Advanced Battery Technology Ltd. | Fire and corrosion resistant thermally stable electrodes and batteries and method for manufacturing same |
| US20040053136A1 (en) * | 2002-09-13 | 2004-03-18 | Bauman William C. | Lithium carbide composition, cathode, battery and process |
| WO2004047202A1 (en) * | 2002-11-18 | 2004-06-03 | Kejha Joseph B | Cathode compositions and method for lithium-ion cell construction having a lithium compound additive, eliminating irreversible capacity loss. |
| US20060121352A1 (en) * | 2002-11-18 | 2006-06-08 | Kejha Joseph B | Cathode compositions and method for lithium-ion cell construction having a lithum compound additive, eliminating irreversible capacity loss |
| US9048494B2 (en) * | 2010-08-03 | 2015-06-02 | Erachem Comilog, Inc. | Electrolytic manganese dioxide improved for tool wear reduction |
| US8883350B2 (en) | 2010-11-25 | 2014-11-11 | Basf Se | Process for preparing precursors for transition metal mixed oxides |
| KR20140013069A (en) * | 2011-06-13 | 2014-02-04 | 가부시키가이샤 히타치세이사쿠쇼 | Lithium secondary battery |
| DE102015211110A1 (en) | 2015-06-17 | 2016-12-22 | Robert Bosch Gmbh | Active material for a cathode of a battery cell, cathode and battery cell |
| JP6805940B2 (en) * | 2017-04-03 | 2020-12-23 | トヨタ自動車株式会社 | Lithium-ion secondary battery and its manufacturing method |
| DOP2018000132A (en) * | 2018-05-24 | 2018-10-31 | Intec | STABILIZED POSITIVE ELECTRODE OF MANGANESE LITHIUM OXIDE FOR SECONDARY LITHIUM BATTERY AND THE METHOD FOR PRODUCTION. |
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|---|---|---|---|---|
| JP2002117843A (en) * | 2000-10-05 | 2002-04-19 | Sony Corp | Nonaqueous electrolyte secondary battery |
| JP2008181830A (en) * | 2007-01-26 | 2008-08-07 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery |
| JP2011159576A (en) * | 2010-02-03 | 2011-08-18 | Hitachi Maxell Energy Ltd | Lithium ion secondary battery |
| KR20130121132A (en) * | 2010-11-25 | 2013-11-05 | 바스프 에스이 | Process for preparing precursors for transition metal mixed oxides |
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| Publication number | Publication date |
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| JP3562187B2 (en) | 2004-09-08 |
| US6022641A (en) | 2000-02-08 |
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